Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/19—Hydroxy compounds containing aromatic rings
  • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
  • C08G67/04—Polyanhydrides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C09D167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings

Definitions

• the present invention relates to powder components, coating resin compositions and coating films.
• Patent Document 1 describes a film-forming resin mainly composed of a polyester composed of a residue of a divalent carboxylic acid having a biphenyl structure, a diphenyl ether structure and a cyclohexane structure, and a residue of a dihydric phenol. It is described that by controlling the free divalent carboxylic acid to 0.01 to 300 ppm, the electrical properties can be stabilized when applied to capacitors, electrophotographic photoreceptors, and the like.
• the present inventors found that when a coating film was formed using a conventional powder component containing polyarylate, the transparency of the coating film was poor.
• an object of the present invention is to provide a powder component, a coating resin composition, and a coating film capable of forming a coating film with excellent transparency.
• a coating resin composition comprising the powder component according to any one of [3] and a solvent.
• the present invention it is possible to provide a powder component, a coating resin composition, and a coating film capable of forming a coating film with excellent transparency.
• a numerical range represented by “to” means a range including the numerical values before and after “to” as lower and upper limits.
• substituents, linking groups, etc. that do not specify whether they are substituted or unsubstituted are in the sense that the groups may have appropriate substituents. be. Therefore, in this specification, even when simply described as “- group” (eg, "alkyl group”), this "- group” (eg, "alkyl group”) is a substituent.
• each constituent when a polymer has a plurality of constituents with the same designation (indicated by the same general formula), each constituent may be the same or different.
• the powder component of the present invention is a polyarylate containing a repeating unit represented by formula (A-I) and a repeating unit represented by formula (A-II), and a compound different from the polyarylate,
• a powder component containing a compound having a repeating unit represented by formula (B) (hereinafter also referred to as “compound B"), A value obtained by subtracting measured value 1 from measured value 2 (hereinafter also referred to as “X value”) is 2000 mass ppm or less.
• Measured value 1 Mass ratio of the compound represented by the formula (C) (hereinafter also referred to as "compound C") in the powder component to the total mass of the powder component.
• Measurement value 2 The ratio of the mass of compound C in the mixture obtained by mixing the powder component and diethylamine to the total mass of the powder component.
• powder component means a powdery component. It should be noted that the powdery form also includes granular and pelletized forms. Also, even if the powder component contains a liquid component, it is included in the powder component as long as the powder component is powdery as a whole.
• a characteristic point of the powder component of the present invention is, for example, that the X value is within a predetermined range.
• the X value substantially represents the content ratio of the compound B, and the present inventors controlled the range of the X value (in other words, the content ratio of the compound B) to control the powder component. It was found that the transparency of the coating film is excellent when the coating film is formed by using. Hereinafter, more excellent transparency of the coating film is also referred to as more excellent effects of the present invention.
• the powder component of the present invention will be described in detail below. First, the X value will be described, and then the compounds contained in the powder component will be described in detail.
• the X value is a value obtained by subtracting the measured value 1 from the measured value 2.
• compound B contains an acid anhydride group (--CO--O--CO--), so when mixed with diethylamine, this acid anhydride group portion is cleaved to form --CO--N ( C 2 H 5 ) and a group represented by HO--CO--.
• Compound C which will be described later, has groups (a group represented by —CO—N(C 2 H 5 ) and a group represented by HO—CO—) generated by cleavage of compound B above.
• compound C is a compound derived from the repeating unit represented by formula (B) in compound B, which is generated by cleavage of the acid anhydride group with diethylamine. Therefore, the mass of compound C resulting from this mixing with diethylamine corresponds substantially to the mass of compound B in the powder component, and the X value substantially corresponds to the mass of compound B relative to the total mass of the powder component. represents a percentage.
• Measured value 1 is the ratio (%) of the mass of compound C in the powder component to the total mass of the powder component.
• the mass of the compound C originally contained in the powder component (for example, the compound derived from the residual monomer, etc.), not the compound C generated by the decomposition of the compound B with diethylamine, is the X value. It is a value to eliminate addition. In other words, measurement 1 is the blank value.
• Measured value 2 is the ratio of the mass of compound C in the mixture obtained by mixing the powder component and diethylamine to the total mass of the powder component.
• Measured value 2 is obtained by mixing diethylamine and a powder component to prepare a mixture, decomposing compound B contained in the powder component with the diethylamine, determining the mass of compound C in the mixture, and calculating the mass of the powder component. It is a value obtained by measuring the ratio of the obtained mass of compound C to the total mass of.
• the ratio (%) is calculated by adding the total mass of the compound C originally contained in the powder component and the compound C which is a decomposed product of the compound B. Therefore, by subtracting the measured value 1, which is the blank value, from the measured value 2 (measured value 2 ⁇ measured value 1), the X value corresponding to the mass ratio of compound C, which is a degradation product of compound B, can be calculated.
• the X value is 2000 mass ppm or less, preferably 1500 mass ppm or less, more preferably 1000 mass ppm or less, even more preferably 500 mass ppm or less, and even more preferably 100 mass ppm or less.
• the lower limit is more than 0 mass ppm in many cases, and is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, and even more preferably 10 mass ppm or more from the viewpoint of easy production of the powder component.
• the supernatant liquid is measured by HPLC. Specifically, 50 mg of the powder component is dissolved in 2 mL of tetrahydrofuran. Thereafter, methanol is added to a constant volume of 10 mL, and the supernatant obtained by reprecipitating the polyarylate is filtered through a filter to obtain a filtrate.
• a good solvent such as THF
• a poor solvent such as MeOH
• HPLC analysis is performed using an ODS column as a separation column, water containing phosphoric acid and acetonitrile as an eluent, and a sample injection amount of 10 ⁇ L.
• a photodiode array detector is used as the detector, and the detection wavelength is 254 nm to determine the ratio (%) of the mass of compound C to the total mass of the powder components.
• HPLC analysis is performed using an ODS column as a separation column, water containing phosphoric acid and acetonitrile as an eluent, and a sample injection amount of 10 ⁇ L.
• the detection device uses a photodiode array detector, the detection wavelength is 254 nm, the mass of compound C in the mixture obtained by mixing the powder component and diethylamine is obtained, and the total mass of the powder component ( The ratio (%) of the mass of compound C to the mass of the powder component charged in the mixture is determined.
• the content of compound C is detected by HPLC analysis, it may be calculated using the calibration curve as described above.
• Methods for adjusting the X value include, for example, a method of separately adding compound B, a method of increasing the purity of raw materials for producing polyarylate, a method of adjusting polymerization conditions for polyarylate, and an amine treatment described later. mentioned.
• the method using the raw material of high purity for example, it is preferable that the purity of the compound b from which the repeating unit represented by the formula (A-II) is derived is high.
• Examples of the structure of compound b include compounds represented by formula (A-IIb).
• the content of 4,4′-biphenyldicarboxylic acid and/or 4-(4-carboxyphenyl)-benzoic acid chloride is 4,4′-biphenyldicarbonyl chloride. It is preferable to use less raw material relative to the total mass of carbonyl chloride. Specifically, the content of 4,4′-biphenyldicarboxylic acid and/or 4-(4-carboxyphenyl)-benzoic acid chloride is 5% with respect to the total mass of 4,4′-biphenyldicarbonyl chloride.
• the amine treatment is a treatment in which an amine compound is added to the powder component to decompose the compound B. By the amine treatment, the compound B is decomposed and the content of the compound B in the powder component can be reduced.
• the amine compound is preferably a primary amine compound or a secondary amine compound from the viewpoint of facilitating reaction with the compound B, and more preferably a secondary amine compound from the viewpoint of suppressing a side reaction with the polyarylate.
• the amine compound preferably has a small molecular weight, and the amine compound is more preferably diethylamine.
• the powder component includes a repeating unit represented by formula (AI) and a polyarylate containing a repeating unit represented by formula (A-II).
• L 11 represents a group represented by -Ar 11 -(L 12 -Ar 12 ) n -.
• Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon ring.
• L 12 represents a single bond, an oxygen atom, a sulfur atom or -C(R 11 )(R 12 )-.
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group. R 11 and R 12 may combine with each other to form a ring.
• n represents an integer of 1 or more.
• L 21 represents a group represented by -X 21 -(L 22 -X 22 ) m -.
• X 21 and X 22 each independently represent an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a linear hydrocarbon group.
• L 22 represents a single bond, an oxygen atom, a sulfur atom or -C(R 21 )(R 22 )-.
• R21 and R22 each independently represent a hydrogen atom or an alkyl group. R 21 and R 22 may combine with each other to form a ring.
• m represents an integer of 0 or more.
• L 11 represents a group represented by -Ar 11 -(L 12 -Ar 12 ) n -.
• Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon ring.
• the above aromatic hydrocarbon ring may be either monocyclic or polycyclic.
• the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6-30, more preferably 6-12, even more preferably 6-8.
• the aromatic hydrocarbon ring may have a substituent. Examples of the substituent include groups exemplified for the substituent T, and an alkyl group, a cycloalkyl group, or an aryl group is preferable.
• Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring and anthracene ring, with benzene ring being preferred.
• L 12 represents a single bond, an oxygen atom, a sulfur atom or -C(R 11 )(R 12 )-.
• L 12 is preferably a single bond or -C(R 11 )(R 12 )-, more preferably -C(R 11 )(R 12 )-.
• R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group. R 11 and R 12 may combine with each other to form a ring.
• the above alkyl group may be linear, branched or cyclic.
• the number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-15, and even more preferably 1-5.
• Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group and methylbutyl group.
• the aryl group may be monocyclic or polycyclic.
• the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms.
• aryl group examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group, methylphenyl group, dimethylphenyl group, biphenyl group and fluorenyl group, with phenyl group being preferred.
• At least one of R 11 and R 12 preferably represents an alkyl group, more preferably both R 11 and R 12 represent an alkyl group, and one of R 11 and R 12 represents a linear alkyl group. and the other preferably represents a branched alkyl group.
• the ring formed by combining R 11 and R 12 include an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring and the aliphatic hydrocarbon ring include aromatic hydrocarbon rings and aliphatic hydrocarbon rings represented by X 21 and X 22 described later. Also, R 11 and R 12 preferably do not form a ring.
• n represents an integer of 1 or more. n is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1. When multiple Ar 12 are present, the multiple Ar 12 may be the same or different. When multiple L 12 are present, the multiple L 12 may be the same or different.
• L 21 represents a group represented by -X 21 -(L 22 -X 22 ) m -.
• X 21 and X 22 each independently represent an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a linear hydrocarbon group.
• the aromatic hydrocarbon ring include the aromatic hydrocarbon rings represented by Ar 11 and Ar 12 described above.
• the above aliphatic hydrocarbon ring may be either monocyclic or polycyclic.
• the number of carbon atoms in the aliphatic hydrocarbon ring is preferably 3-30, more preferably 3-6.
• Examples of the aliphatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring and cyclohexane ring.
• the straight-chain hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
• a linear alkyl group is preferable as the linear hydrocarbon group.
• L 22 represents a single bond, an oxygen atom, a sulfur atom or -C(R 21 )(R 22 )-.
• L 22 is preferably a single bond, an oxygen atom or —C(R 21 )(R 22 )—, more preferably a single bond or an oxygen atom.
• R21 and R22 each independently represent a hydrogen atom or an alkyl group.
• R 21 and R 22 may combine with each other to form a ring.
• R 21 and R 22 include, for example, hydrogen atoms or alkyl groups represented by R 11 and R 12 described above. Examples of the ring formed by combining R 21 and R 22 include the ring formed by combining R 11 and R 12 described above.
• n represents an integer of 0 or more. m is preferably an integer of 0 to 3, more preferably 0 or 1, and more preferably 1.
• polyarylates examples include polyarylates containing repeating units represented by the following formula (AI) and repeating units represented by the following formula (A-II). First, specific examples of the repeating unit represented by formula (A-1) are shown.
• repeating unit represented by formula (A-II) Specific examples of the repeating unit represented by formula (A-II) are shown below.
• the weight average molecular weight of the polyarylate is preferably 50,000 to 250,000, more preferably 80,000 to 180,000, even more preferably 100,000 to 150,000.
• the weight-average molecular weight is a polystyrene-equivalent molecular weight obtained by gel permeation chromatography (GPC).
• the polyarylate content is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly preferably 99.9% by mass or more, relative to the total mass of the powder component.
• the upper limit is preferably less than 100% by mass with respect to the total mass of the powder component.
• the content of the repeating unit represented by formula (AI) is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, more preferably 30 to 60% by mass, based on the total repeating units of the polyarylate. More preferred.
• the content of the repeating unit represented by formula (A-II) is preferably 10 to 60% by mass, more preferably 20 to 55% by mass, more preferably 30 to 50% by mass, based on the total repeating units of the polyarylate. More preferred.
• Compound B is a compound different from polyarylate, a compound having a repeating unit represented by formula (B), and compound b from which the repeating unit represented by formula (A-II) is derived, It is a compound produced by a reaction.
• Compound B is a compound different from polyarylate, and is preferably a compound having only repeating units represented by formula (B) as repeating units. “Different from polyarylate” means that compound B does not have the repeating unit represented by formula (AI) and the repeating unit represented by formula (A-2).
• L 31 represents a group represented by —X 31 —(L 32 —X 32 ) q —.
• X 31 and X 32 each independently represent an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a linear hydrocarbon group.
• L 32 represents a single bond, an oxygen atom, a sulfur atom or -C(R 31 )(R 32 )-.
• R 31 and R 32 each independently represent a hydrogen atom or an alkyl group.
• R 31 and R 32 may combine with each other to form a ring.
• q represents an integer of 0 or more.
• L 31 represents a group represented by -X 31 -(L 32 -X 32 ) q -.
• Examples of L 31 include groups represented by L 21 .
• —X 31 —(L 32 —X 32 ) q — represented by L 31 , X 31 , L 32 , X 32 and q are respectively X 21 , L 22 , X 22 and m is synonymous with and preferred embodiments are also the same.
• repeating units represented by formula (B) include the following repeating units.
• the molecular weight of compound B is preferably 450 to 30,000, more preferably 700 to 20,000, even more preferably 1000 to 10,000.
• the above molecular weight is the weight average molecular weight.
• the weight average molecular weight can be measured by the same method as for the weight average molecular weight of the polyarylate described above.
• the content of compound B is preferably substantially the same as the content of compound C described later.
• Compound C is a decomposition product derived from compound B produced by mixing the powder component and diethylamine, and is a compound represented by formula (C).
• Z 41 and Z 42 each independently represent -OH or -N(C 2 H 5 ) 2 .
• L 41 represents a group represented by -X 41 -(L 42 -X 42 ) r -.
• X 41 and X 42 each independently represent an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a linear hydrocarbon group.
• L 42 represents a single bond, an oxygen atom, a sulfur atom or -C(R 41 )(R 42 )-.
• R41 and R42 each independently represent a hydrogen atom or an alkyl group.
• R 41 and R 42 may combine with each other to form a ring.
• r represents an integer of 0 or more.
• Z 41 and Z 42 each independently represent —OH or —N(C 2 H 5 ) 2 .
• L 41 represents a group represented by -X 41 -(L 42 -X 42 ) r -.
• Examples of L 41 include groups represented by L 21 .
• —X 41 —(L 42 —X 42 ) r — represented by L 41 , X 41 , L 42 , X 42 and r are respectively X 21 , L 22 , X 22 and m is synonymous with and preferred embodiments are also the same.
• Examples of compound C include the following compounds.
• L 21 , L 31 and L 41 represent the same group.
• L 31 and L 41 are L 21 in two or more repeating units represented by formula (A-II). is selected from any of the groups constituting
• the polyarylate contains repeating unit A and repeating unit B, which correspond to repeating units represented by formula (A-II)
• L 31 and L 41 in formula (B) are repeating unit A and L 21B in repeating unit B (L 21A and L 21B ) .
• L 21 , L 31 and L 41 are preferably a group represented by any one of formulas (L-1) to (L-5) or a combination thereof, and represented by formula (L-1) is more preferred.
• a group obtained by combining them means a group obtained by combining two or more groups represented by any one of formulas (L-1) to (L-5). The two or more groups may be the same or different.
• the powder component may contain other components in addition to the various components described above.
• Other components include, for example, residual monomers, residual solvents, phase transfer catalysts and amine compounds.
• substituent T examples include the following groups. alkyl group (preferably alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl and 1-carboxymethyl), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl and oleyl), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl and phenylethynyl), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl and 4-methylcyclohexyl), aryl groups (preferably aryl groups having 6 to 26 carbon atom
• R P is a hydrogen atom or a substituent (preferably a substituent exemplified by the substituent T).
• substituents exemplified for these substituents T may further have substituents exemplified for the substituents T described above.
• the coating resin composition of the present invention contains the powder component described above and a solvent.
• the powder ingredients are as described above.
• solvents include water and organic solvents, with organic solvents being preferred.
• organic solvents include dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene and m-dichloroethane.
• Chlorinated solvents such as chlorobenzene; Aromatic hydrocarbon solvents such as toluene, benzene and xylene; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 1,4-dioxane, and tetrahydrofuran is preferred.
• the coating resin composition may contain other additives in addition to the various components described above.
• Other additives include, for example, known additives.
• the method for producing the powder component of the present invention is not particularly limited, and known methods can be used.
• Examples of the method for producing polyarylate include known methods for producing polyarylate.
• interfacial polymerization between a divalent carboxylic acid halide and a divalent phenol can be mentioned.
• the interfacial polymerization includes a method of adding a mixed solution or slurry containing a divalent carboxylic acid halide and an organic solvent to an alkaline aqueous solution containing a divalent phenol; A method of adding directly to a mixture containing an alkaline aqueous solution containing a dihydric phenol, a polymerization catalyst and an organic solvent for the organic layer is preferred.
• a solid such as a powder of a divalent carboxylic acid halide
• the content of the solvent is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total mass of the divalent carboxylic acid halide.
• the lower limit is often 0% by mass or more relative to the total mass of the divalent carboxylic acid halide.
• the powder component of the present invention may be prepared by mixing the polyarylate produced by the procedure as described above and the separately produced compound represented by the formula (B). Alternatively, the polyarylate and the compound represented by the formula (B) may be produced simultaneously by adjusting the conditions for producing the polyarylate.
• the method for producing the powder component may include other steps in addition to the above.
• Other processes include, for example, a raw material refining process and a powder component refining process.
• the raw material refining step is a step of refining the raw material used as the raw material of the powder component.
• a known purification method may be used for the above purification method.
• the powder component refining step is a step of further refining the powder component after obtaining the powder component.
• a purification method of reprecipitating the powder component by adding a poor solvent such as methanol after dissolving the obtained powder component in a good solvent such as tetrahydrofuran is preferable.
• the content of compound B and the content of compound C can be adjusted.
• Other steps may be used singly or in combination of two or more. Other steps may be performed once or twice or more.
• the coating film is a film formed using the coating resin composition described above.
• the coating film preferably contains various components other than the solvent that can be contained in the coating resin composition.
• the coating film may be a coating film combined with a functional material.
• Coating films combined with functional materials include, for example, low moisture permeability films described in JP-A-2016-069468.
• a low-moisture-permeable film is a film in which a phenolic compound is added as a functional material to a polyarylate, thereby exhibiting high compatibility between the polyarylate and the functional material and effectively suppressing moisture permeability.
• the coating film is also suitably used as, for example, a metal wire coating film and a polarizing plate protective film for display devices.
• the coating film may be used with other layers placed on it.
• durability can be further enhanced by forming a protective layer in contact with the coating film.
• the method of forming the coating film is not particularly limited as long as it is formed using the coating resin composition.
• a coating resin composition may be applied onto a substrate and the coating film may be dried to form a coating film.
• the coating method and the drying method include a known coating liquid coating method and a known coating film drying method.
• the substrate is not particularly limited, and a wide range of materials and members having surfaces to be coated can be applied.
• Powder component A-1 was produced by the following experimental procedure.
• Powder component A-1 corresponds to Examples. 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.) (43.10 g) and triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ( 33.06 g) was added with methylene chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (260 mL) to prepare a solution.
• the obtained component containing polyarylate was re-dissolved in tetrahydrofuran (3000 mL) and then poured into methanol to reprecipitate the component containing polyarylate.
• the precipitated component containing polyarylate was filtered, washed with methanol, and dried at 50° C. to obtain powder component A-1 (68.9 g) containing polyarylate A-1.
• Measurement value 1 is obtained by dissolving powder component A-1 (50 mg) in tetrahydrofuran (2 mL). After that, methanol is added to a constant volume of 10 mL, and the supernatant obtained by reprecipitating polyarylate A-1 is filtered through a filter to obtain a filtrate.
• HPLC analysis is performed using an ODS column as a separation column, water containing phosphoric acid and acetonitrile as an eluent, and a sample injection amount of 10 ⁇ L.
• a photodiode array detector was used as a detection device, and the detection wavelength was 254 nm.
• Measured value 2 is obtained by dissolving the powder component (50 mg) in tetrahydrofuran (2 mL) and then adding diethylamine (10 ⁇ L). After that, methanol is added to a constant volume of 10 mL, and the supernatant obtained by reprecipitating polyarylate A-1 is filtered through a filter to obtain a filtrate. Using the obtained filtrate, HPLC analysis is performed using an ODS column as a separation column, water containing phosphoric acid and acetonitrile as an eluent, and a sample injection amount of 10 ⁇ L. A photodiode array detector was used as a detection device, and the detection wavelength was 254 nm.
• the repeating unit represented by formula (B) and compounds C1-1 to C1-3 possessed by polyarylate A-1 and compound B-1 are shown below.
• the unit of numerical values in parentheses in polyarylate A-1 is mol %.
• Powder component A-2 was produced by the following experimental procedure.
• Powder component A-2 corresponds to Examples. 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.) (43.11 g) and triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ( 33.06 g) was added with methylene chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (260 mL) to prepare a solution.
• 4,4′-Biphenyldicarbonyl chloride (HPLC purity 99.0%) (45.23 g) in the form of powder was added to this solution at a temperature of 5° C. while stirring. After completion of the addition, the temperature of the solution was raised to 30° C. and stirred for 4 hours under a nitrogen atmosphere to allow the polymerization reaction to proceed. Further, the solution after polymerization was subjected to the following purification treatment. The resulting solution was further diluted with tetrahydrofuran (3000 mL), and then methanol was introduced into the solution to precipitate the polyarylate-containing component. A component containing the precipitated polyarylate was filtered, washed with methanol, and dried at 50°C.
• the obtained component containing polyarylate was re-dissolved in tetrahydrofuran (3000 mL) and then poured into methanol to reprecipitate the component containing polyarylate.
• the precipitated component containing polyarylate was filtered, washed with methanol, and dried at 50° C. to obtain powder component A-2 (68.0 g) containing polyarylate A-2.
• the X value was obtained by subtracting the measured value 1 from the measured value 2 using the powder component A-2 in the same procedure as the measurement with the powder component A-1.
• the repeating unit represented by formula (B) and compounds C2-1 to C2-3 possessed by polyarylate A-2 and compound B-2 are shown below.
• the unit of numerical values in parentheses for polyarylate A-2 is mol%.
• Powder component A-3 was produced by the following experimental procedure.
• Powder component A-3 corresponds to Examples. 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.) (43.10 g) and triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ( 33.06 g) was added with methylene chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (260 mL) to prepare a solution.
• 4,4′-biphenyldicarbonyl chloride (HPLC purity 98.5%) (45.46 g) in the form of powder was added to this solution while stirring at a temperature of 5°C. After completion of the addition, the temperature of the solution was raised to 30° C. and stirred for 4 hours under a nitrogen atmosphere to allow the polymerization reaction to proceed. Further, the solution after polymerization was subjected to the following purification treatment. The resulting solution was further diluted with tetrahydrofuran (3000 mL), and then methanol was introduced into the solution to precipitate the polyarylate-containing component. A component containing the precipitated polyarylate was filtered, washed with methanol, and dried at 50°C.
• the obtained component containing polyarylate was re-dissolved in tetrahydrofuran (3000 mL) and then poured into methanol to reprecipitate the component containing polyarylate.
• the precipitated component containing polyarylate was filtered, washed with methanol, and dried at 50° C. to obtain powder component A-3 (67.5 g) containing polyarylate A-3.
• the X value was obtained by subtracting the measured value 1 from the measured value 2 using the powder component A-3 in the same procedure as the measurement with the powder component A-1.
• Compounds C3-1 to C3-3 which will be described later, correspond to the compound C used when calculating the measured value 2.
• the repeating unit represented by formula (B) and compounds C3-1 to C3-3 possessed by polyarylate A-3 and compound B-3 are shown below.
• the unit of numerical values in parentheses for polyarylate A-3 is mol%.
• ⁇ Powder component A-4> In a reaction vessel equipped with a stirrer, 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry) (11.45 g), 2,3,5-trimethylphenol (Tokyo Kasei Kogyo (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.1750 g), sodium hydrosulfite (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (0.0572 g), and water (230 mL) were added to form a suspension.
• 2,2-bis(4-hydroxyphenyl)-4-methylpentane manufactured by Honshu Chemical Industry
• 2,3,5-trimethylphenol Tokyo Kasei Kogyo (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (0.1750 g)
• sodium hydrosulfite manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• water 230 m
• Dichloromethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (210 mL) was added to this aqueous solution, and after stirring for 30 minutes under a nitrogen atmosphere, 4,4′-biphenyldicarbonyl chloride (HPLC purity 99.5%) (12.00 g) was added as powder. After completion of the addition, the temperature was brought to room temperature (20° C.) and the reaction was allowed to proceed with stirring for 4 hours under nitrogen atmosphere. The post-polymerization solution was diluted with dichloromethane (300 mL) and the aqueous phase was removed.
• the X value was obtained by subtracting the measured value 1 from the measured value 2 using the powder component A-4 in the same procedure as the measurement with the powder component A-1.
• the repeating unit represented by formula (B) of polyarylate A-4 and compound B-4 and compounds C4-1 to C4-3 are shown below.
• the unit of numerical values in parentheses for polyarylate A-4 is mol%.
• Powder components A-5 to A-8 were prepared in the same manner as powder component A-1.
• Powder components A-5 to A-8 contained compounds B-5 to B-8, respectively.
• the X value was obtained by subtracting the measured value 1 from the measured value 2 for each compound C using each powder component in the same procedure as the measurement for the powder component A-1.
• each polyarylate A and each compound B and each compound C are shown below.
• the unit of numerical values in parentheses for each polyarylate A is mol %.
• Powder component A-9 was prepared by the following experimental procedure.
• Powder component A-9 corresponds to a comparative example.
• 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.) (43.10 g) and triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ( 33.06 g) was added with methylene chloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) (260 mL) to prepare a solution.
• the obtained component containing polyarylate was re-dissolved in tetrahydrofuran (3000 mL) and then poured into methanol to reprecipitate the component containing polyarylate.
• the precipitated component containing polyarylate was filtered, washed with methanol, and dried at 50° C. to obtain powder component A-9 (69.2 g) containing polyarylate A-9.
• the X value was obtained by subtracting the measured value 1 from the measured value 2 using the powder component A-9 in the same procedure as the measurement with the powder component A-1.
• the repeating unit represented by formula (B) of polyarylate A-9 and compound B-9 and compounds C9-1 to C9-3 are shown below.
• the unit of numerical values in parentheses for polyarylate A-9 is mol %.
• ⁇ Heat resistance evaluation> When comparing the mass of the evaluation sample before heating with the mass of the evaluation sample after heating to 200 ° C. using a differential thermal / thermogravimetric simultaneous measurement device (TG / DTA), the evaluation after heating The mass reduction rate of the sample was measured to evaluate the heat resistance.
• the sample for evaluation was placed in an aluminum pan and measured while the temperature was raised at 10° C./min in a nitrogen atmosphere.
• B The mass reduction rate at 200°C is 0.5% by mass or more
• X value is a value obtained by subtracting measured value 1 from measured value 2.
• Mw indicates the weight average molecular weight of the polyarylate.
• the weight-average molecular weight is a polystyrene-equivalent molecular weight obtained by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the powder component of the present invention provides films with excellent transparency. It was confirmed that when the X value was 1000 ppm by mass or less, the heat resistance was more excellent (Examples 1 to 5). Also, from a similar comparison, it was confirmed that heat resistance and transparency are more excellent when the X value is 500 ppm by mass or less.

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